Azodyestuffs containing chromium



Patented Sept. 15, 1936 UNITED STATES PATENT OFFICE,

AZODYESTUFFS CONTAINING CHROM'IUM Richard Stiisser, Cologne-Deutz, Germany, as-

signor to General Aniline Works, Inc., New York, N. Y a corporation of Delaware No Drawing. Application January 27, 1933, erial No. 653,927. In Germany February 2,

932 2 Claims. (Cl. 260- 12) The present invention relates to new azodyeable organic base, wherein those compounds con stuffs containing chromium in a complex form taining the base in the molecule may besides conand to intermediate-products used in the manutain water in their molecule, and wherein the facture of the said dyestuffs, more particularly it benzene nucleus may bear further substituents,

relates to azodyestuffs which are derived from the such as alkyl-, 'alkoxy, the nitro group, halogen 5" 4-amino-l-hydroxybenzene-Z-carboxylic acid and and the sulfonic acid group. j f its nuclear substitution products as diazotization As non-diazotizable bases which may be present components. in my newcomplex compounds there may be The l-amino-l-hydroxybenzene 2 carboxylic mentioned by way of example primary, secondary acid and its nuclear substitution products yield and tertiary aliphatic bases and secondary and 10 diazo compounds which can be coupled with tertiary aromatic bases, such as ethylenediamine, coupling components suitable for producing azodibutylamine, piperidine, tributylami'ne, ethyldyestuffs. The energy for coupling of these diazo aniline, dimethylaniline, pyridine and quinoline'.

compounds, however, is so low that they only do The complex chromium compounds of the l. 15 couple with components easily coupling. Thus, type: 5

for example, up to the present it is not possible COOH at all or only difficultly possible to couple the ldiazo compounds of 4-amino-1-hydroxybenzene- Cr DONE; 2-carboxylic acids with Z-hydroxynaphthalene- 6 L 2 6,8-disulfonic acid, with 2-hydroxynaphthalene- 4,8-disulfonic acid or with 2-hydroxynaphthalene 3,6 disulfonic acid, or with 2 hydroxynaphthalene-8-sulfonic acid, with salicylic acid or with cresotinic acid.

Now I have found that the energy of coupling diazo-compounds of l-amino-l-hydroxybenzene- Z-carboxylic acid and. its nuclearlsubstitution products is highly increased when diazotizing complex chromium compounds of the same, which are obtainable by heating, for example, by refiuxing, the 4-amino-1-hydroxybenzene-2-carboxylic acids in the free form or in form of a watersoluble salt, especially an alkali metal 'salt', with a water-soluble chromium salt/containing chromium in the trivalent form, such as chromium 25 chloride, chromium fluoride, chromium sulfate, chromium acetate, chromium formatejin wateror in an organic solvent, such as alcohol, or in a complex compounds can be diazotized in the usual g jgg i sisal f a orgamc g f f a 30 n nts titliitliffiltifh522%;22332? W e of @hmmm It is one feature of my invention to produce for producing the chrommm complex chromium complex compounds of pounds corresponds to molecular equivalent for hydroxybenzene-2-carboxylic acids and of its 1 molecular proportlon of the 4'ammo 1- 35 hydroxybenzene-Z-carboxylic acid. However, it should be mentioned that the process can be per-' formed with excess chromium salt or with less than the theoretical quantity, in the former case the excess chromium remaining in the reaction 40 mass, while in the latter case only part of the 4- nuclear substitution products, such as alkyl-,

alkoxy-, nitro-, halogenand sulfonic acid substitution products. These new complex compounds may be represented by the probable gen- 40 eral formula:

(30011 I I amino-1-hydroxybenzene-2-carboxylic acid being transformed into the chromium complex com- 7 a From the reaction mass the complex com- Wherem X Stands for the group pounds either wholly or partially separate in form 45 of their salts as yellowish to grey to brownish: OH powders, or they remain in solution, in which latter case their solutions can be used directlyjin 5.0 OH I nuiae 9i azodyastufia,

' r Those chromium complex compounds containing a non-diazotizable organic base in the molecule are-obtainable by treating the 4-amino -1-;

1 hydroxybenzene-2 carboxylic acids ora; water 5.5; in which latter group .3 stands for a non-diazotizsoluble salt thereof in water pr,in an, organic;

2 F lowish to brown substances, while those contain- .ing water'generally are obtained in form of colormedium, suchas alcohol, or in an aqueous organic medium, with a chromium salt. of the kind referred to above and with the addition of a nonseparate in a crystalline form, or 7 tion. r 1 Those complex compoundsofr'ee from water are diazotizable base. Favorably the reaction is carried out with the application" of heat, for example, by refluxing. However, the reaction may also be carried out at room temperature, for example, by stirring at room temperature for a prolonged time, say for several days. V

In carrying out the invention care is to be taken ,that for one molecular proportion of 4-amino-1- .hydroxybenzene-2 carboxylic acid at least 1 molecular proportion of the non-diazotizable base is present, generally, however, I am working with an excess of the non-diazotizable base.

The quantity of the chromium salt required 7 corresponds to thatused in the. manufacture of the complex compounds freefrom the base.

from the reaction mass the new chromium complex compounds containing chromium and a non-diazotizable base either wholly' or partially remain in solu hijform of their alkalimet'al salts generally yelless, to violet to" weakly brownish substances. j From my present knowledge I cannot say that the Constitution as stated above of the new complex compounds, is correct; from the analysis of the 'chromium-pyridine-complex compounds of 4 amino 1 hydroxybenzene-2-carboxylic acid however, it may be'concluded that these compounds correspond to the formulae:

F F [UL (2.1L

' (Py= pyridine) respectively, from which the general formulas disclosed above would result. 7

From my new complex; compounds azodyestuffs are; obtainable by tetrazotizing the same in the usual'm'anner and coupling with two molecular proportions: of a coupling component suitable for producing azodyestuff. The new dyestuffs which may be represented by the probable general formula: V r

wherein X stands. for the group or a in which latter group B standsfor a non-diazotizable organic base, and wherein'R stands for the radical of; a coupling component suitable for pro-'-' ducing an azodyestuff', are in form of their alkali metal salts generally water-soluble substances.

The shades obtained with the dyestuffs vary myeuow tored "toviolet to blue to black, de pending upon the specific coupling'componen-ts' and specific substituents present'in the diazo-- tizationcomponent used.

By treating the new dyestuffs in solution with a caustic alkali or with a strong acid,'such'as hydrochloric acid or sulfuric acid, or formic acid or oxalic acid, the chromium or the base and the. chromium respectively are removed from the dyestuffs, it being mentioned that the base is more easily, split 011 than the chromium, and that therefore from the dyestuffs containing chromium and base also the dyestuffs containing chromium are obtainable.

By splitting off .the'chromium or the chromium and the base, one molecule of the dyestufi of the formula coon wherein X means, the same as above yieldsatwo molecules of a dyestuffof the formula: coon V The invention is illustrated by the following examples, without being limited thereto:

Example 1.-2 3fl grams of 4-amino-l-hydroxy- 7 benzene-Z-carboxylic acid are refluxed for about three hours in 500 ccsaof water with 250 ccs.- of

pyridine and 250 grams of an aqueous chromium chloride solution ofa strength corresponding to' 270 grams of ch03 in one liter; During the reaction a brownish-violet chromium-pyridine com pound of. the 4-amino-l-hydroxybenzene-2-care boxylic acid separates. When the reaction is COOH complete, the new complex compound is filtered with suction, washed with water and dried. It is a crystalline substance of the molecular formula: C24H31N4O11C1, and probably has the following constitution:

C OOH )11 a r (HzO) Cr GONE: I L V I l Py z .t

' 7 It can be diazotized in the usual manner, for ex V ample, with sodium nitrite and hydrochloric or sulfuric acid, yielding a reddish-brown crystalline diazo compound, easily soluble in. water and coupling with coupling components to form azod-yee stuffs. The energy of coupling is highly increased compared with that of diazotized 4-amino-1-hydroxybenzehe-Z-carboxylic acid.

When working in the same manner but without the addition of. an organic base, there is obtained a grey chromium complex compound,

probably corresponding to the. following for-' mula "coon 1:

Example 2.--230 grams of 4-amino-1-hydroxybenzene-Z-carboxylic acid are refluxed for about coon IlOONHZ It is difficultly soluble in water, easily soluble in aqueous soda solution or in aqueous ammonia. It can be diazotized in the usual manner yielding a red brown crystalline diaz o compound, which is easily soluble in water and couples with coupling components to form azodyestuffs.

Example 3.30 grams of 4-amino-6-methyl-- l-hydroxybenzene-Z-carboxylic acid are refluxed for about 3 hours in 40 cos. of water with 40 cos. of pyridine and 21 ccs. of an aqueous chromium chloride solution of a strength corresponding to 2'70 grams of ClzOz in one liter. In the course of the reaction a brownish crystalline mass separates. When the reaction is complete, the complex compound formed is filtered with suction, washed with water and dried. It has properties similar to those of the substance obtainable in accordance with Example 1.

Example 4. grams of 6-sulfo-4-amino-1- hydroxybenzene-Z-carboxylic acid are refluxed for about 3 hours in 50 cos. of water with 30 ccs. of triethanolamine and 21 cos. of an aqueous chromium sulfate solution of a strength corresponding to 290 grams of CI2O3 in one liter. When the reaction is complete, the reaction mixture is allowed to cool, and the chromium triethanolamine complex of 6-sulfo-4- amino-l-hydroxybenzene-2-carboxy1ic acid compound formed is precipitated by salting out. After filtering and drying it is obtained as a greenish-grey substance, soluble in water and which can be diazotized in the usual manner.

Example 5.l grammolecular proportion of the complex chromium pyridine compound of 4- amino-l-hydroxybenzene-2-carboxylic acid, prepared according to Example 1, is covered. with a mixture of 750 grams of glacial acetic acid and 200 grams of hydrochloric acid of 22 B. strength, and the complex compound is,diazotized by adding thereto 700 cos. of a 10% aqueous sodium nitrite solution, the temperature thereby being maintained at about 5 C. When the diazotization is complete, some ice is added and the mass is slowly introduced into a solution containing ice prepared from two grammolecular proportions of salicylic acid and 480 grams of caustic soda, 950 grams of an aqueous caustic soda lye of 38 B. strength being simultaneously added and care being taken that during the whole coupling ice is present in the reaction mixture and that the solution reacts caustic alkaline during the whole process. The formation of the dyestufr immediately begins and is soon complete. When the diazo compound is no more detectable, hydrochloric acid is added in order to neutralize the caustic soda. The chromium compound of thedyestufi which hasbeen precipitated by the addition of the hydrochloric acid and which probably corresponds to the following formula:

is filtered with suction and dried. It dyes wool light yellow shades which by afterchrorning becomes more red and more powerful. The afterchromed shades are very fast to fulling.

Example 6.The dyestuff obtained by coupling one molecular proportion of the diazotized complex chromium-dimethylaniline compound of 4 amino-l-hydroxybenzene-2-carboxylic acid and two molecular proportions of G-methyl-l-hydroxybenzene-2 carboxylic acid and having in its free state probably the following formula:

dyes wool yellow shades which by after-chroming become deeper and fast to fulling.

Example 7.One molecular proportion of the complex chromium pyridine compound obtained in accordance with Example 1, is diazotized as described in Example 5, and coupled in aqueous soda solution with two molecular proportions of 2-hydroxynaphthalene-8-sulfonic acid. The coupling is soon complete, the azodyestuif formed is salted out, filtered and dried. It is a dark powder, soluble in water with a red coloration, dyeing wool yellowish shades. In its'free state it probably has the following formula:

A dyestuff having similar properties is obtained when substituting the chromium pyridine complex compound by the corresponding chromium triethanolamine complex compound.

Example 8.-By coupling one molecular proportion of the diazotized chromium complex com'- pound, obtainable by refluxing 4-amino-1-hydroxybenzene-Z-carboxylic acid with chromium chloride in water with the addition of sodium acetate, with two molecular proportions of 2- hydroxynaphthalene-3;6-disulfoni'c acid; there is obtained a dyestuffi of the; probable formula;

. i GOOH OH SOaE Hi V V I n I: S OaH a being soluble in water, dyeing wool red shades.

The dyestufi is further suitable for being pre- 7 cipitated by means of barium carbonate; yielding a bluish-red lake fast to water. V 7

Example 9.One molecular proportionof' the complex chromiumrcompound prepared inaccord-- "mice with Example 4 frome-amino-l hydroxybenz'ene- 2'-carboxylic acid-G-sulfonic acid i'sdia-zotized' and coupled in aqueous caustic soda solution with two molecular proportions of salicylic acid.

' The azodyestuff separated corresponds in its free state to the probable formula coon : r on 1 limo-empire 1- 01 0 By treating the azodyestufi with a mineral acid the base, and the chromium are removed from the dyestufi. The dyestuff free from chromium and the base. thus obtained dyes wool light yellow shades-which by after-chroming yield a clear yellow fast to fulling.

'By coupling the diazotized complex chromium compound of 4-amino-1-hydroxybenzene-2-can boxylic acid with '1-hydroxybenzene-2-carboxylic acid-fisulfonic acid there is obtained a: dyestufi having similar properties.

7 Besides the coupling. components used in the preceding examples other coupling components can be used, such as aminoand diamino-ben- 7' zenes, hydroxyand diaminonaphthal'eneaj hyphenols, aminoand 'diaminonaphthalenes, hy-

droxyand dihydroxynaphthalenes, aminonaphthols,, amino-l and. hydroxy-carbazoles and coupling components containing a methylene group. 7 with a reactive hydrogen atom such as pyrazo- Tones, acylacetic acid arylamides methylketol' and the like. 7 o r i If the dyestufis obtained inaccordance with my COOH V V I invention still contain a diazotizable amino group 7 the new 'azodyestufls. canbe further diazotized and coupled; with coupling components.

I claim: V 1'. The azod-yestufi's of; the general formula:

soon i wherein X stands for one of the groups G: Am.

and

in which latter group B stands for a non-diazoti'zable organic base, wherein R stands. for the radical; of a coupling: component suitable for-producing: azodyestuffs and. wherein Y stands for a member of the group consisting of hydrogen, alkyl, alkoxmnitro, halogen and the sulf'oni'c; acid group; 2. The azodyestufis of the general formula;

wherein R stands for the radical of a coupling,

component suitable for producing azodyestufls and wherein Y stands for a member of the; group consi'sting of hydrogen, alkyi, alkoxy, nitro, halogen and the sulfonic acid groups.

RICHARD s'riissER. 5o 7 

